Process of producing cementitious material



Patented May 28, 1935 PROCESS OF PRODUCING CEMENTITIOUS MATERIAL Gilbert A. Hoggatt, Buffalo, N. Y., assignor to Certain-Teed Products Corporation, New York, N. Y., a corporation of Maryland No Drawing.

11 Claims.

This invention relates to the manufacture of calcined gypsum andcontemplates a new process whereby a calcined gypsum product is obtained which requires less water to bring it,'in mixing,

to the consistency desired fora workable slurry or mortar than is required by the calcined gypsum manufactured under standard procedure at present. 7

An object of this invention is to control the 10 water carrying capacity of calcined gypsum so that fora given gypsum rock a calcined product with any desired water carrying capacity, within reasonable limits, may be obtained. The water carrying capacity? is the amount of Water, calculated as percentage by weight of the dry material, which is necessary to bring the mixture to testing consistency; In my prior application Serial No. 601,285, filed March 25, 1932, and now matured into Patent No. 1,960,538 which is a continuation in'part of my prior application Serial No, 312,937, filed October 16, 1928, I have set forth a definition of :testing consistency accepted as standard at the time of filing said application Serial No. 312,937., :Bythis defini:

In practice it isfound, depending upon the 35. quality, age and other conditions of thecalcined gypsum, that one hundred parts of calcined gypsum require from 65 to 100 parts of water byweight, in order to produce a slurry of pouring. consistency as required for casts or molds.

40 This calcined gypsum enters into chemicalcome bination with 16 to of its own weight of,

water, as water of crystallization, in setting or hardening. It isapparent that a large percentage of water is left to be eliminated by evaporation orlby absorption by the mold. in order to produce the desiredproduct in its dry, set and hardened 'form. In other'words, for every 109 grams of calcined gypsum requiring 70 grams of water to produce a slurry of pouring consistency, approximately 54 to '45 grams of water by evaporation or absorption by the mold must be eliminated from a cast' made fromsuch a slurry. This results, in the formation of cells or ,voids in the finished product to such an extent as to materially reduce its density and strength.

Application March 1, Serial No.-713,617

tion a neat, mortar mixture is. of testing con- A low water carrying capacity is necessary where high density and strength of" the resulting products are important. The-smaller the amount of water required to produce aslurry or mortar, the denser and stronger is the resultant cast.

Heretofore it commonly has been the practice to' producecalcined gypsum of reduced water carrying capacity by manufacturing the calcined gypsum according to the usual rcalcining' process and storing the product forfa period of'time. 10 It has been found by experience that during the time of storage the characteristics of the gypsum are modified insuch a way that its .watercarry .ing capacity is reduced from that which it possesses immediately upon completion of cal- '15 cination. Such modification of the water ca'rry-' ing capacity is termed the natural ageing. of the calcined gypsuma The process of natural ageing requires considerable time and is sub' ject to uncontrollable variations due to the 20 changes in atmospheric conditions. i

Another object, therefore, of the present invention is to provide a process of treating gypsum, preierably during the process of calcination;

whereby the water carryingcapacity of the cal- 25,

cined gypsum is reduced by virtue of the eiTect which certain materials have on the gypsum during calcination. Moreover, 'by the use of this process the water carrying capacity of the calcined gypsum produced maybe controlled by'a variation inthe amount of these materials present during calcination.

I have discovered in calcining gypsum rook-to produce calcined gypsum that the admixtureto the gypsum to be calcined or the addition thereto while being calcined of certain substances which will lower .the calcining temperature, that i is, the decomposition'or inversion temperature, of the gypsum will lower the water .carrying'ca- 'pacity of the calcined gypsum. fThe decompo- 40 sition or inversion temperature, as it. is under stood in connection with water of crystallization of salts .and' other compounds which take up water in forming crystals, is the temperature at which the'fvapor pressure of the water of crystallization of the salt or of the compoundisj equal to or just exceeds the partial pressure of the water vapor in the surroundingmedium or equals or exceedsthe saturation pressure it the medium is saturated with water vapor. -In the case of gypsumbeing calcined under standard calcining procedure the pressure'in the apparatus is substantially'atmospheric pressure since intsuch a standard process the ground gypsumv isv heated in a kettle open to the atmosphere or the form molecular solutions in water.

kettle is maintained at atmospheric pressure and the calcining process is carried on by heating the kettle without permitting substantial rise of the pressure within the kettle in driving off the water of crystallization from the gypsum. However, the partial pressure of the water vapor in the kettle maybe less than the pressure of saturated water vapor at the temperature existing within the kettle. The process of my invention, however, does not depend upon the use of any particular pressureand the results may be obtained in calcining processes operating at pressure other than atmospheric pressure.

I have found by adding the substance 'of the character above mentioned to the gypsum at such a time in its preparation for calcining as will insure the presence of the substance withi'n'th'e kettel during calcination, that I may obtain the reduction of the decomposition temperature. This reduction, whether itself a cause of the lowering of the water carryingcapacity of the calcined gypsumoronly,as an incidental phenomenon, is characteristic and indicative of the effect upon the calcining process and upon the water carrying capacity of the calcined product of calcining the gypsum in the presence of such a substance. I am aware that the use of deliques'cent chlorides of certain alkaline earth metals heretofore hasbeen proposed to produce aged calcined gypsum, In my co-pending app1ication,:Serial No. 601,285 above mentioned, I have disclosed the use of certain alkali compounds including the alkali salts of the inorganic acids, which alkali compounds are of the type which I have included among said alkali compounds those compounds, whetheralkalis or alkali salts, which are non-deliquesoent. In said prior application No. 601,285 I have disclosed and claimed the use of alkali compounds containing a halogen, including the halogen compounds of the alkali metals or of their equivalent, the ammonium radical, whether or not said halogen compounds are deliquescent or non-deliduescent.v The invention of the present application relates to certain subject matter included in the disclosure of said prior application, Serial No. 601,285, of which the present application is a division. The invention of the present application relates to the use of an inorganic acid'containing a halogen, and particularly to the use of the halogen acids, said acid being admixed with the gypsum so as to be present during calcination for the .purpose of lowering the. decomposition temperature and securing a product having a low water carrying capacity as above described.

I have found that the halogen acids are effective for the purpose of my invention as above set forth and particularlyhydrochloric acid because of its cheapness and availability as compared with other acids containing halogens. Results similar to those obtained with hydrochloric acid, however, are to be expected in using hydrobromic and hydriodic'acids. Moreover, I also contemplate within my invention mixtures of these acids. 7

By careful tests with such substances in calcininggypsum I havefound that a marked reduction in the water carrying capacity of the calcined gypsum is effected. For example, I have found that the normal water carrying capacity for a certain freshly calcined gypsum calcined Without the use of such reagents is '72 as tested by the method defined above. Bythe use of one of the reagents, for example hydrochloric in water and placed in a suitable container.

for. the reduction of the decomposition or inversion temperature of the gypsum are among those which lower the vapor pressure of water when in solution therein, and while the relation of these phenomena is not so apparent as entirely to ex plain the result obtained, namely, the reduction of the'water carrying capacity of the calcined gypsum, nevertheless, by my experiments and tests I have effectively reduced the water carrying capacity of the calcined product and thus accomplished the desired artific'1al ageing of the calcined gypsum, that is, the reduction of its water carrying capacity by so calcining the gypsum at the reduced decomposition temperature produced by the presence of such reagents.

This new" process is of economic importance, because it facilitates the manufacture or production of calcined gypsum of desired water car rying capacity at low temperatures and in short periods of time. Heretofore, calcined gypsum of low water carrying capacity has been manufactured by prolonged periods of calcination, calcination at high temperatures, or by natural ageing of the calcined products, as above mentioned. The two former processes involve expenditures of heat andtime and result in increased expense for fuel and labor. The latter process, as stated above, is dependent on weather conditions and upon the temperature and humidity of the atmosphere as well as upon storage conditions, and is, moreover, very expensive in that large stocks of calcined gypsum must be. kept idle for considerable periods of time. By the present invention a calcined gypsum product of reduced water carrying characteristics is obtained upon completion of calcination and with' a minimum expenditure of heat, time and labor. Moreover, the :process can be so controlled as to produce within limits any desired water carrying capacity. My invention, however, may be used in combinationwith any of the former processes to still further reduce or to suitably modify the water carrying capacity obtained by such processes.

As an illustration of one manner in which I carry out my process I may introduce into the kettle or any other type of calcining equipment during calcination, the selected halogen acid which forms the re-agent used according to the present invention. In practice, a predetermined amount of the selected re-agent may be dissolved This containermay be equipped withcompressed air connections and connections to a spraying device,

carrying capacity of 68 when tested upon completion of the calcining operation:

Pounds of re- Water carryagent per ton Percent of ing capacity of calcined re-agent of the calgypsum clned product In general the amounts of re-agent for practical results may be between 1 pound and 3 pounds per ton of calcined product. These amounts are not intended to be definite limits but to indicate the general practical range of the relation of the re-agent to the calcined product. By varying the amount of acid for a given rock any desired water carrying capacity can be obtained, within reasonable limits In the regular calcination process when no reagent is present, the gypsum boils or calcines for about forty minutes at about 240 to 250 Fahrenheit. When a re-agent of my invention is present, for instance in amounts of from 1 to 3 pounds per ton of calcined product, the boiling temperature drops to a range of about 235 to 225 Fahrenheit, indicating that the decomposition temperature of the gypsum is lowered by the presence of the re-agents. In some instances I have found that the presence of the re-ag'ents in greater or less proportions than from one to three pounds per ton is necessary to achieve the desired result. Similar results may be obtained with the other re-agents of the type described above as included in my invention.

What I claim as new is:

1. The process of manufacture of calcined gy sum which comprises calcining gypsum, and adding to the gypsum before completion of the calcining operation a halogen acid.

2. The process of manufacture of calcined gypsum Which comprises calcining gypsum, and spraying into'contact with the gypsum as it is being calcined, a water solution of a halogen acid.

3. The process of manufacture of calcined gypsum which comprises calcining gypsum, and adding hydrochloric acid to the gypsum before completion of the calcining operation.

4. The method of controlling the water carrying capacity of calcined gypsum which comprises adding a halogen acid to the gypsum as it is being calcined, and varying in accordance with variations in said water carrying capacity of the calcined gypsum produced the amount of halogen acid brought into contact with the gypsum being calcined.

5. The method of controlling the decomposi- 7 tion temperature of gypsum during the process of calcination of gypsum to produce calcined gypsum which comprises adding to the gypsum so as to be present during the calcination a predetermined amount of a halogen acid.

6. The method of controlling the water carrying capacity of calcined gypsum which comprises delivering into contact with the gypsum being calcined an amount of a halogen acid controlled in a predetermined ratio to the amount of gypsum being calcined.

7. The process of manufacture of calcined gypsum which comprises calcining gypsum, and

adding hydrobromic acid to the gypsum before sum which comprises calcining gypsum, and.

adding hydriodic acid to the gypsum before completion of the calcining operation.

9. The process of manufacture of calcined gypsum which comprises calcining gypsum, and adding to the gypsumbefore completion of the calcining operation an inorganic acid containing a halogen.

10. The method of controlling the water carrying capacity of calcined gypsum which comprises adding to thegypsum as it is being calcined an inorganic acid containing a halogen, and varying in accordance with variations in said Water carrying capacity of the calcined gypsum produced the amount of said inorganic acid containing a halogen which is brought into contact with the gypsum being calcined.

11. The method of controlling the water carrying capacity of calcined gypsum which commined ratio to the amount of the gypsum being calcined.

GILBERT A. HOGGATT. 

